DE1932646A1 - 1-Isoalkylamino-5-alkoxy- and -5-hydroxyanthraquinones and their preparation - Google Patents

Description

1932646 FARBENFABRIKEN BAYER AG

LEVERKUSEN-B * yerwerk 2 June 6, 1969 Patent department

Double room / wi.

1-Isoalkylamino-5-alkoxy- and 5-hydroxy-anthraquinones and their preparation

The invention relates to new compounds of the general formula

(D

and a method for their production.

In the formula (I), R ₁ and R ₂ independently of one another denote optionally substituted lower alkyl radicals having 1-3 carbon atoms and R denotes hydrogen or a lower optionally substituted alkyl radical having 1-5 carbon atoms.

Examples of alkyl radicals R ₁ and Rg are: methyl, ethyl, propyl, hydroxymethyl, ß-hydroxyethyl, ß-cyanoethyl, ß-chloroethyl, ß-.y-dihalopropyl, such as ß - ^ - Dibromopropyl residues.

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Examples of possible radicals R- are: methyl, ethyl, ß-hydroxyethyl *, ß-methoxyethyl, ß-xthoxyethyl, ß- (ß ^f -methoxy-ethoxy) -ethyl-J ß- (ß '-Ethoxy-ethoxy) -ethyl-; n- or iso-propyl, n- or iso-butyl radicals.

The compounds according to the invention are valuable intermediates to build up new, organic dyes. The corresponding new dyes are obtained, for example, if one compounds of the general formula (I) in the p-position to the isoalkylamino group of the anthraquinone ring system, e.g. in dilute mineral acids or in inert organic solvents at room temperature or slightly "Monobrominated at elevated temperature and then the bromine atom, for example, against amines, acid amides or Exchange mercaptans.

The new compounds of the formula (I) are prepared by adding compounds of the general formula

(II)

or their alkali salts, preferably the sodium or Potassium salts, at elevated temperature with alkali hydroxides, preferably sodium or potassium hydroxide, and alcohols the general formula

R ₃ ¹ OH, (III)

where R- ^{1 represents} an optionally substituted lower alkyl radical,

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reacted and the compounds of the formula thus obtained

0 NH-GH

² > (IV)

wherein R ₁ , Rp and R-, ^{1 have} the meaning already given,

optionally treated with aqueous mineral acids, preferably hydrous sulfuric acid, at elevated temperature. If dilute sulfuric acid is used as the aqueous mineral acid, the HpSO.-concentrations are between about 60 and about 80 # are particularly suitable.

Temperatures of 60 ° for the reaction of the compounds of formula (II) - 120 ⁰ C suitable. In general, 0.1 to 0.8, preferably 0.2 to 0.5, moles of alkali metal hydroxide are used per mole of alcohol R ^ ^{1 OH.} The response time can be varied within wide limits; In the case of 1 molar batches, the setting time can be 1/2 to 4 hours. By suitable choice of temperature, reaction time, type of alcohol and the alkali metal hydroxide / alcohol R, ¹ OH ratio, either a selective replacement of the sulfonic acid group by the alkoxy group or predominantly by the hydroxyl group can be achieved, with either compounds of the formula (IV) or (I), R, = optionally substituted lower alkyl radical with 1-3 C atoms, or compounds of the formula (I), R, = hydrogen. In this way, mixtures of 1-Ieoalkylamino-5-alkoxy- and i-Isoalkylamino-5-hydroxyanthraquinones of various compositions can also be prepared.

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Instead of alkali metal hydroxides and alcohols, it is of course also possible to use the corresponding alcoholates in the reaction .

The already mentioned bromination for the production of further Valuable intermediates for the construction of new anthraquinone dyes can of course directly in the Connection to the acidic saponification in the same reaction vessel be carried out to, for example, i-isoalkylamino-5-hydroxy-4-bromo-anthraquinone to manufacture.

Starting compounds of the formula (II) for the process according to the invention are, for example, 1-isopropylamino-, 1-sec.-. fc butylamino-, pentylamino- (3 ') - »1 ^f -hydroxybutylamino- (2') - anthraquinone-5-sulfonic acid or its alkali metal salts. They can be obtained by reacting anthraquinone-1,5-disulfonic acid sodium with isopropylamine, sec-butylamine, 3-aminopentane, 1-hydroxy-2-aminobutane in an aqueous medium in the presence of an oxidizing agent such as m- Nitrobenzenesulfonic acid sodium and optionally with the addition of magnesium oxide and catalytic amounts of a copper salt, such as copper II sulfate in the autoclave at temperatures of 110 ° - ΐ50 ° 0, such as for the sodium salt of i-isopropylamino-anthraquinone-5-sulfonic acid in the Belgian patent 729 177 described.

P The alcohols IU'OH are for the reaction according to the invention e.g. suitable methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether

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Compounds of formula (I) ,. wherein R * is hydrogen may also by a known method by so-called Kalkdruckschmelze, ie, reaction of compounds of formula (II) with an aqueous solution of calcium oxide and magnesium chloride under pressure at temperatures of 180 ° - 220 ⁰ C are obtained. This process is described in French patents 336,867 and 336, for example.

The process according to the invention offers several advantages over the process of pressure lime melting, ao the greater range of applications, which also includes, for example, the preparation of the azoxy compounds of the formula (I), where R- is a lower, optionally substituted alkyl radical having 1-5 C atoms; furthermore the reaction temperatures which are lower by more than 100 ^° C. and which allow the reaction to be carried out without pressure; finally, better space-time yields and purer end products.

The parts given in the examples are, as far as nothing otherwise indicated, parts by weight. The temperatures are degrees Celsius.

example 1

a) 160 parts of FaOH are dissolved in 600 parts by volume of methanol at the boiling point and in this solution with intensive care Stirring at 80 ° 200 parts of 1-isopropylaminoanthraquinone-5-sulfonic acid Fatrium (89 # -ig) so quickly entered that the melt always remains easily stirrable (about 30 minutes required). Now it is heated to 80 ° - 85 ° (approx * 30 minutes) until one is removed and chromatographed sample only trace white Binsatssmaterial is detectable. One dilutes with

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1000 parts of hot water, sucks off at 70 ° - 80 °, washes neutral with hot water and dry in vacuo.

135 parts (95% of theory) of I-isopropylamino-5-methoxy-anthraquinone are obtained, which still contains 2% of 1-isopropylamino-5-hydroxy-anthraquinone.

b) 100 parts of the product obtained according to a) are stirred into 200 parts by volume of 70% sulfuric acid and Stirred at 120 ° until no input material can be detected chromatographically in a sample taken is (about 2 1/2 hours required). It is now diluted at 50 ° -60 ° with 100 parts of water, waiting for one

ψ Precipitation has occurred, heat up to 90 ° - 95 ° with the slow addition of another 30 parts of water and stir in the cold for approx. 15 hours. The product, which has separated out as crystalline crystals, is filtered off with suction through a G3 Pritte, and the filter material is washed with 50% H ₂ SO. until it is clear, pale yellow, stirs it into 500 parts of cold water, sucks it off, washes neutral and dries. 87 parts of i-isopropylamino-5-hydroxyanthraquinone (91.5 # of theory), which contains 1 # 1-amino-5-hydroxyanthraquinone, are obtained.

c) Comparative test according to the French method Patents 336,867 and 336,938 (Ealkdruckschmelze); 220 parts of i-isopropylamino-anthraquinone-5-sulfonic acid Sodium, 144 parts of ground calcium oxide, 161 parts of 28 # magnesium chloride solution and 1,780 parts of water are heated to 200-210 ° in a stirred autoclave for 18 hours.

One sucks off and the nuts are washed with hot water almost neutral, mix it in 1000 parts of water, add 1000 parts by volume of 30% hydrochloric acid, stir for as long

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at 95 ° - 100 °, until all Ca-Salt has been broken down (approx. 1 hour required), sucks off, washes neutral with hot water and dries. 149 parts are obtained = 91 i » d.Th. of i-isopropylamino-S-hydroxy-anthraquinone. The product contains more impurities than that obtained according to Example 1b, for example significantly more 1-amino-5-. hydroxy anthraquinone.

d) In Example 1a, instead of 600 parts by volume of methanol, a mixture of 550 parts by volume of methanol + 50 parts is used Water, 1-isopropylamino-5-methoxy-anthraehinone is also obtained in very good yield.

Example 2

If you work as described in Example 1a, but instead of 160 parts of NaOH, 210 parts of sodium methylate are used, eo 1-isopropylamino-S-methoxy-anthraquinone is also obtained in almost quantitative yield.

Example 3

In an iron kettle with anchor stirrer and reflux condenser, a solution of 9.1 parts of NaOH in 36 parts of methanol and 4 parts of ethylene glycol monomethyl ether prepared. In these Solution is carried at 75 ° -80 ° within 2 hours with stirring, 20 parts of i-isopropylamino-anthraquinone-5-sulfonic acid Sodium (94 S * -ig), stirred for 1 hour at 83 ° - 85 °, fills the kettle with hot water, sucks on a stone nutsche, washes neutral with hot water and presses sharply off. 24.4 parts of press cake with a water content of 40.7 ^ are obtained.

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This press cake is introduced into 34.7 parts of 90% sulfuric acid with vigorous stirring, and the solution is heated to 120 ° - 125 °, until no more i-l-bopropylamino-5-methoxy-anthraquinone is found in a processed sample by chromatography is detectable (approx. 3 hours required), diluted at 50 ° - 80 ° with 18 parts of water, stirs cold overnight, sucks off the sulphate, which has precipitated in large boat-shaped plates, washes it with 50 # sulfuric acid, breaks it down it with water, washes neutral and dries. 12.9 parts (90% of theory) of i-isopropylamino-5-hydroxyanthraquinone are obtained.

Example 4

a) The procedure is as described in Example 3, but after dilution with 18 parts of water, not suctioned off as described there, but 10.6 parts of bromine are added with vigorous stirring at room temperature and the mixture is stirred, optionally at one to 40 ° increased temperature until less than 5% 1-isopropylamino-5-hydroxy-anthraquinone can be detected in a sample taken, processed and chroraatographed. It is diluted with 95 parts of water, stirred for some time, reduced unreacted bromine with the amount of bisulfite liquor just necessary, filtered off with suction, washed neutral and dried. 17.4 parts of isopropylamino-4-bromo-5-hydroxy-anthraquinone are obtained, that is 94 % of theory. based on i-isopropylamino-anthraquinone-S-sulfonic acid sodium.

b) Dissolve the 12.9 parts of i-isopropylamino-5-hydroxy-anthraquinone obtained in Example 3 in 130 parts 30 # hydrochloric acid and 9.5 parts dropwise at room temperature Bromine is added and the mixture is stirred at room temperature or at an elevated temperature (up to 40 °) until in one

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removed. Sample chromatographically no more than 5 $> i-isopropylamino-5-hydroxy-anthraehinone are detectable, after pouring onto 300 parts of water and further work-up as described in a), 15 | 95 parts of 1-isopropylamino-S-hydroxy-bromine are obtained -anthraquinone. The quality of this product is only slightly better than that of the product obtained according to Example 4a.

c) 36 parts of i-isopropylamino ^ -bromo ^ -hydroxy-anthraquinone, obtained according to Example 4b, are introduced into 108 parts of molten p-toluenesulfamide at 150 ° and the resulting 25 parts of potassium acetate and 0.7 parts of basic copper acetate are added to the solution. Takes place in an exothermic reaction rapid conversion, the temperature is allowed to rise to 165 °. If chromatographically in a sample taken no more feed material can be detected (approx. 30 minutes required), the melt is diluted briskly with 150 parts of methanol, the reaction product precipitated in coarse crystals sucks at 50 ° -60 ° and washes it with boiling hot methanol until the clear blue run-off, then with hot water. To 33.7 parts of i-l-propylamino-4-p-toluenesulfamido-5-hydroxy-anthraquinone are dried obtain.

This product, in finely divided form, dyes polyester fibers in a violet-blue tone using conventional dyeing processes.

d) 10 parts of the product obtained according to Example 4c are treated in 100 parts of 70% strength sulfuric acid at 60 ° until no more starting material can be detected by chromatography in a sample taken (approx. 30 minutes required). You give up while stirring

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1000 parts of cold water, sucks the precipitate obtained, washes neutral and dries. 6.5 parts of i-isopropylamino- ^ amino-S-hydroxy-anthraquinone are obtained.

This product dyes - in finely divided form, synthetic Polyamide and polyester fibers in blue tones.

e) 2 parts of the product obtained according to Example 4d are added to 20 parts of 12 # strength oleum at room temperature for as long stirred until only traces of the starting material can be detected by chromatography in a processed sample are.

After applying to dilute saline solution, neutralize with alkali and washing with dilute saline solution, the sodium salt becomes a monosulfonic acid of 1-isopropylamino-4-amino-5-hydroxy-anthraquinone obtained, the natural and synthetic polyamide fibers by common dyeing processes colors in blue tones.

Example 5

a) In an open flask are 42 parts of NaOH in 150 parts Ethylene glycol monomethyl ether dissolved at 80 ° - 90 °, too 45 parts of 1-isopropylamino-anthraquinone-5-sulfonic acid are added to this solution at 70 ° with vigorous stirring Sodium briskly too. It is stirred at the same temperature for 20 minutes, diluted with 200 parts of water, Sucked off, washed neutral with boiling water and dried at 60 ° in a vacuum. 30 parts are obtained 1 -Isopropylamino-S-w-methoocy-ethoxy-anthraquinone, the

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2 - 3 $> contains i-isopropylamino-S-hydroxy-anthraquinone.

b) 5 parts of the product obtained according to a) are _{stirred in 50 parts of 75 # H 2} SO _{4 for} 75 minutes at 120 ° -125 ° and then diluted at 50 ° -60 ° with enough water that a 50 ° S- ige HpSO. is present. The precipitated sulfate crystals are filtered off with suction at room temperature, washed with about 45% H _? SO ,, decomposes the sulfate with water, washes neutral and dries. 3 »4 parts of i-isopropylamino-5-hydroxyanthraquinone are obtained. During the saponification, i-Isopropylamino-5-ß-hydroxyethoxy-anthraquinone can be detected temporarily by chromatography «

Example 6

a) In an open flask, 42 parts of NaOH are dissolved in 150 parts of diethylene glycol monomethyl ether to form this solution

45 parts of 1-isopropylamino-anthraquinone-5-sulfonic acid sodium are quickly added at 60 °, the mixture is stirred at the same temperature for 30 minutes and worked up as described in Example 5a. 30.6 parts of 1-isopropyl -5-β- ( ^ω- methoxy-ethoxy) -ethoxy-anthraquinone are obtained.

b) By saponification analogously to Example 5b, 3.3 parts of 1-isopropylamino-5-hydroxy-anthraquinone are obtained from 5 parts of the compound obtained according to Example 6a obtain.

Example 7

a) In a solution of 100 parts of KOH in 300 parts of ethylene glycol, 100 parts of finely powdered 1-isopropylamino-

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Anthraquinone-5-sulfoneBauresodium, stir for 20 minutes at the same temperature, add 15 parts of water, heated to reflux, if necessary add 5-10 parts of water after 1-2 hours and hold on for as long Reflux, "until removed in one, chromatographed Only a small amount of sulfonic acid can be detected in the sample (time required depending on the distribution of the 1-isopropylamino-anthraquinone-5-sulfonic acid used Sodium 1 1 / 2-4 hours).

The mixture is stirred cold, diluted slowly with 300 parts of water, and the precipitated in crystalline form is sucked well The reaction product which can be sucked off, washes it neutral with hot water and dries.

I-Isopropylamino-5-hydroxy-anthraquinone is obtained, which is free from i-Isopropylamino-S-alkoxy-anthraquinone.

b) If in a) one sets an equally large one instead of ethylene glycol Amount of ethylene glycol monomethyl ether is obtained in a similar reaction also 1-isopropylamino-5-hydroxy-anthraquinone, which contains small amounts of 1-isopropylamino-S-u-methoxy-ethoxy-anthraquinone.

Example 8

a) In a solution of 17 parts of NaOH in 60 parts by volume 20 parts of ground 1-butylamino- (2 ') -anthraquinone-5-sulfonic acid are added to methanol at 85 ° Sodium and stir at the boiling point until little of the sulfonic acid can be detected in a sample by chromatography is. It is diluted with 200 parts of hot water, filtered off with suction, washed neutral with hot water and dried.

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H »6 parts of 1-butylamino- ( ^2r ) -5-methoxyanthraquinone, which contains small amounts of 1-butylamino- (2 ') -5-hydroxy-anthraquinone, are obtained.

b) 13 »6 parts of the product obtained according to a) are in 130 parts by volume of 70 # HgSO. 1 hour at 120 ° - 125 ° heated, diluted with enough water that a 30 # acid is present and the resulting precipitate is sucked off, washed neutral and dried. 11 parts of 1-butylamino- (2 ') -5-hydroxy-anthraquinone are obtained.

Example 9

If you work as in Example 9a, but instead of 20 parts of 1-butylamino- (2 ^! ) -Anthraquinone-5-sulfonic acid sodium, an equal amount of 1-pentylamino- (3 ') - anthraquinone-5-sulfonic acid sodium is obtained 1-Peritylamino- (3 ^I ) -5-methoxy-anthraquinone and, by saponifying it analogously to Example 8b, 1-pentylamino- (3 ^f ) -5-hydroxy-anthraquinone.

Example 10

18 parts of finely powdered 1- (1'-hydroxybutylamino- (2 ')) -anthraquinone-5-sulfonic acid sodium are stirred into a solution of 21 parts of NaOH in 70 parts by volume of methanol and heated to 90 ° until there is no feedstock more is detectable (approx. 15 minutes required). It is diluted with water, filtered off with suction while warm, washed neutral and dried. A mixture of 1- (1'-hydroxybutylamino- (2 ')) -5-hydroxy-anthraquinone and 1- (1 ^f -hydroxybutylamino- (2)) -5-methoxy-anthraquinone is obtained. The latter compound can be converted into the hydroxy compound by saponification with 65% sulfuric acid.

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Example 11 IV

a) 90 parts of KOH are added to 155 parts by volume of methanol

Dissolved 90 °, 50 parts are slowly added at 70 ° - 80 ° i-Isopropylamino-anthraehinone-S-sulfonic acid sodium too and stirred for 2 hours at 90 °. It is added to 1000 parts of water, acidified with concentrated HCl, and washed hot neutral and dries. 36.2 parts of a mixture of predominantly 1-isopropylamino-5-methoxyanthraquinone are obtained and i-isopropylamino-S-hydroxy-anthraquinone.

b) If the mixture obtained according to a) is saponified analogously to Example 1b), this is obtained with the same work-up i-Isopropylamino-S-hydroxy-anthraquinone with 88 # -iger Yield.

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Claims (10)

Claims; " ^ -4 <compounds of the formula where R .. and R "optionally independently of one another substituted alkyl radicals with 1-3 carbon atoms and R, for hydrogen or a given if substituted alkyl with 1-5 carbon atoms. 2. Process for the preparation of compounds of the formula 0 NH-CH
\ R ₂ where R ₁ and R ₂ independently of one another denote optionally substituted alkyl radicals with 1-3 carbon atoms and R 1 denotes hydrogen or an optionally substituted alkyl radical with 1-5 carbon atoms, characterized in that compounds of the formula HO, S 0
Le A 12 347 - 15 - 10 9 8 i 5 / ζ I 'J 5 wherein R. and R "the" meaning already given to have, or their alkali salts at elevated temperature with alkali hydroxides and alcohols of the formula R ₃ ¹ OH, where R-, 'is an optionally substituted alkyl radical represents with 1-5 C-atoms, converts and the compounds of the formula thus obtained 0 NH - CH Nu - where R ^, Rp and R, ^{1 have} the meaning already given, optionally with aqueous mineral acids at increased Temperature treated. fc 3. The method according to claim 2, characterized in that the reaction with alkali metal hydroxides and alcohols at temperatures of 60 ° - 120 ⁰ C. 4. The method according to claims 2 and 3 »characterized in that that with methanol as alcohol R, 'OH implements.
Le A 12 347 16- 10 98 Ί5 / 2205 5. The method according to claims 2-4, characterized in, that as alkali hydroxides sodium or potassium hydroxide used. 6. Process according to Claims 2-5 _f, characterized in that compounds of the formula O ι
O O NH
ό / ^R 1
- CH
ι ^Vr : ν - ^R 2 "* ■
O wherein R ₁ , and V in the meaning to have, ^ ie * · ^η claim 2 specified treated 150 ⁰ C - with aqueous mineral acids at temperatures of 80 °. 7. The method according to claim 6, characterized in that it is treated with 60-90 # sulfuric acid at temperatures of 110 ° - HO ⁰ C. Le A 12 347 - 17 - 109815/2205